Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/667—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing phosphorus in the main chain
  • D06M15/673—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing phosphorus in the main chain containing phosphorus and nitrogen in the main chain
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/32—Phosphorus-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0066—Flame-proofing or flame-retarding additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
  • D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
  • D01F2/08—Composition of the spinning solution or the bath
  • D01F2/10—Addition to the spinning solution or spinning bath of substances which exert their effect equally well in either
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
  • D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
  • D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
  • D06M11/70—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with oxides of phosphorus; with hypophosphorous, phosphorous or phosphoric acids or their salts
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
  • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
  • D06M13/285—Phosphines; Phosphine oxides; Phosphine sulfides; Phosphinic or phosphinous acids or derivatives thereof
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
  • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
  • D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
  • D06M15/423—Amino-aldehyde resins
  • D06M15/43—Amino-aldehyde resins modified by phosphorus compounds
  • D06M15/431—Amino-aldehyde resins modified by phosphorus compounds by phosphines or phosphine oxides; by oxides or salts of the phosphonium radical
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
  • D06M15/423—Amino-aldehyde resins
  • D06M15/43—Amino-aldehyde resins modified by phosphorus compounds
  • D06M15/432—Amino-aldehyde resins modified by phosphorus compounds by phosphonic acids or derivatives thereof

Definitions

• the present invention reletes of the production of flame-retardant regenerated cellulose fibres by adding one or more flame-retardant phosphorus compounds to viscose, extruding the viscose containing mixture thus obtained into a spinning bath and, if desired, stretching and after-treating the resulting filaments or staple fibres.
• halogen-containing phosphoric acid esters are, however, not entirely suitable for use in the viscose spinning process, in view of their chemical reactivity with the other constituents of the viscose containing mixture, and in view of the fact that they are used in the liquid state. More particularly, the above-mentioned compounds are hydrolyzable in alkaline media, in which they undergo partial decomposition and are deprived of their flame-retardant properties. They have also been found to react with carbon disulphide, which is present in the viscose, with the resultant formation of strongly coloured by-products which impair the external appearance of the resulting fibres and which are difficult to bleach away.
• flame-retardant agents which can be added to regenerated cellulose fibres include phosphonitrile chloride derivatives and phosphonitrilate polymers.
• phosphonitrile chloride derivatives and phosphonitrilate polymers.
• the use of these compounds has been described, for example in U.S. Pat. No. 3,455,713 and Austrian Pat. No. 269,338, respectively.
• These latter compounds have an improved stability to viscose and compare favourably in this property with the halogen-containing phosphoric acid esters first referred to hereinabove. In addition to this, they have been found to affect the fibres' appearance less adversely. Despite this, they are again not fully satisfactory because considerable portions of the compounds go into the coagulating baths, where they are lost, which does not make for economy.
• German published Specification (“Offenlegungsschrift”) No. 1,944,056 describes a process comprising spinning red phosphorus into viscose fibres. In this case, it is possible for red phosphorus to be spun into the fibres practically quantitatively, generally without any adverse effects on the fibre production process. The resulting fibres, however, are dark violet and admit of only limited use in the textile field.
• fibres which retain their flame-retardant property after repeated washing, which are easy to dye, and of which the appearance remains unimpaired under ultraviolet light.
• x stands for a number between 0.9 and 1.7 and y stands for a number between 1.2 and 0, preferably approaching zero as the values of x increase towards 1.7 (component A), with compounds which are selected from phosphoric acid alkyl esters, preferably halogen-containing phosphoric acid alkyl esters; cyclophosphazenes, polyphosphazenes; tetrakis-(oxymethyl)-phosphonium chloride or hydroxide or its condensation products with ammonia, oxymethyl-melamine, urea or other amines or amides; vinyl compounds containing halogen, phosphonitrogen or phosphorus; and tris-(1-aziridinyl)-phosphine oxide or N-(oxymethyl)-3-phosphono-propionamide, if desired in further combination with a condensation resin (component B).
• phosphoric acid alkyl esters preferably halogen-containing phosphoric acid alkyl esters
• the preferred component A representatives are phosphorus nitride, triphosphorus pentanitride, tetraphosphorus hexanitride, and/or phosphorus nitride oxide. It is advisable that the compound(s) used in accordance with the present invention should be solid; thus once they are in pulverulent form, it is possible for them to be dispersed in the viscose or to be spun into the fibres, similarly to titanium dioxide or coloured pigments. The compounds are completely inert with respect to the viscose and the bath used in the viscose spinning process. In clear contrast with some dyestuffs, they could not be found to "bleed out" from the fibres. In other words, they can be incorporated into the fibres substantially quantitatively.
• Preferred component B representatives include: tris-(2,3-dibromopropyl)-phosphate (CH 2 BrCHBrCH 2 O) 3 PO; tris-(2,2'-dichloroisopropyl)-thiophosphate [(CH 2 Cl) 2 CHO]; poly-(isopropoxyphosphazene) - [N ⁇ P ((CH 3 ) 2 (CHO) 2 --] n , in which n stands for a number from 3 to 9.
• the combination of the above component A compounds with the component B compounds has an unexpected result in enabling satisfactory flame-retardant effects to be produced with the use of the combined agent in low proportions within the range about 5 and 22%, based on the quantity of cellulose, i.e. in proportions considerably smaller than those needed for the separate use of the A and B components, respectively.
• this synergism to be based on the fact that the component B compounds commence pyrolyzing activity in the cellulose at temperatures within the range about 220° and 250° C, i.e. at lower temperatures than the component A compounds (about 300° C).
• Such early pyrolysis causes the activity of the component A compounds, which contain considerable nitrogen and phosphorus and accordingly critically determine the flame-retardant effects, to be initiated and promoted.
• component A is always added to viscose and spun therewith, it is possible for component B to be used in various ways.
• the phosphoric acid alkylesters, the cyclo- and polyphosphazenes and the condensation products of tetrakis-(oxymethyl)-phosphonium chloride or hydroxide with ammonia, oxymethylamine, urea or other amines or amides it is possible for them to be used in the form of liquids or pigments and to be added jointly with component A compounds to viscose and to be spun therewith, under customary spinning conditions.
• the component B compounds are vinyl compounds containing halogen, phosphonitrogen or phosphorus of the formula: ##STR1## in which X stands for a hydrogen atom or a methyl group, Y stands for an alkylene group, Z stands for a phosphoric acid alkylester or a mixed phosphoric acid alkylesteramide group, and where the alkylene group Y and the alkyl groups of the phosphoric acid ester or mixed phosphoric acid ester-amide group may contain halogen, the invention provides for those component B compounds to be applied to, and to be chemically combined with, the spun fibres or flat textile structures made therefrom, by polymerization or graft-polymerization, if desired with the aid of a catalyst.
• a further preferred embodiment of the present process provides for the component A compounds to be added to viscose and for the spun fibres or textile structures made therefrom to be impregnated with the component B compounds in the form of a solution of tetrakis-(oxymethyl)-phosphonium chloride or hydroxide or of tris-(1-aziridinyl)-phosphine oxide or of N-(oxymethyl)-3-phosphonopropionamide together with a condensation resin.
• the flame retardant regenerated cellulose fibres made as described hereinabove offer the following beneficial effects.
• the fibres made by the process of the present invention have very good flame-retardant properties and therefore are very useful for making light weight textile materials. These have been made heretofore from fibres which contained high proportions of flame-retardant agents and which naturally affected the articles' general use properties.
• a further beneficial effect of the fibres made in accordance with the present invention, or of flat textile structures made therefrom, resides in the fact that they have a good stability to washing.
• component A 15 weight % (based on cellulose) of triphosphorus pentanitride P 3 N 5 in pigment form (component A) and 5 weight % (based on cellulose) of liquid poly-(isopropoxy)-phosphazene - [N ⁇ P((CH 3 ) 2 CHO) 2 -- ] n , where n stands for a number between 3 and 9, (component B) were metered continuously into a viscose containing 6.5 weight % of cellulose, 6 weight % of alkali, 34 weight % of CS 2 , based on cellulose, and 2 weight % of a modifying agent, based on cellulose.
• the viscose had a viscosity of 80 fbsec.
• the A and B components were very finely distributed in the viscose, which was spun at 40° C into a spinning bath containing 80 g/l of H 2 SO 4 , 120 g/l of Na 2 SO 4 , and 50 g/l of ZnSO 4 .
• the spinning tow which had a total titre approaching 200 000 dtex, was drawn at a rate equal to 100% of its initial length in a second and more dilute spinning bath at 90° C and thereafter cut up in a cutting machine to form staple fibres, which were subjected to the after-treatment customary in the spinning of viscose fibres.
• the conditioned fibres had the following textile properties: Titre: 1.3 dtex; strength of fibre: 24.8 p/tex; elongation: 17%; loop strength: 8.1 p/tex.
• the fabric was washed 50 times at 60° C in a domestic washing machine.
• the flame-retardant properties of the fabric so washed were tested once again, but could not be found to have been impaired.
• the conditioned fibres had the following textile characteristics: Titre: 1.7 dtex; strength of fibre: 25.2 p/tex; elongation: 16.5 %; loop strength: 8.5 p/tex.
• Example 1 The wash test described in Example 1 was repeated. The flame-retardant properties of the fabric could not be found to have been impaired.
• the fleece was impregnated with an iron-II-sulfate catalyst, squeezed off and then impregnated with a hydrogen peroxide-containing aqueous emulsion of diethylphosphatoethylmethacrylate (component B), of which 4 weight % (based on cellulose) was applied to the fleece. Following this, the fleece was conveyed through a zone maintained at high temperatures and subjected to the after-treatment customary in the spinning of viscose fibres.
• component B diethylphosphatoethylmethacrylate
• Titre 1.8 dtex; strength of fibre: 25.8 p/tex;
• the fabric was washed in the manner described in Example 1. Its flame-retardant properties could not be found to have been impaired.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Artificial Filaments (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Compositions Of Macromolecular Compounds (AREA)

Applications Claiming Priority (2)

Publications (1)

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Family Applications (1)

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Cited By (14)

Families Citing this family (1)

Citations (10)

• 1974
  • 1974-08-20 AT AT675974A patent/AT333932B/de not_active IP Right Cessation
• 1975
  • 1975-07-21 CH CH952475A patent/CH582251A5/xx not_active IP Right Cessation
  • 1975-07-29 CA CA232,448A patent/CA1089613A/fr not_active Expired
  • 1975-07-30 SU SU752163066A patent/SU635886A3/ru active
  • 1975-08-05 GB GB32691/75A patent/GB1485533A/en not_active Expired
  • 1975-08-14 US US05/604,489 patent/US4063883A/en not_active Expired - Lifetime
  • 1975-08-18 IT IT50975/75A patent/IT1041259B/it active
  • 1975-08-18 BE BE159273A patent/BE832514A/fr unknown
  • 1975-08-18 DD DD187913A patent/DD119622A5/xx unknown
  • 1975-08-19 BR BR7505286*A patent/BR7505286A/pt unknown
  • 1975-08-19 DK DK374075A patent/DK145187C/da not_active Application Discontinuation
  • 1975-08-19 NL NL7509847A patent/NL7509847A/xx not_active Application Discontinuation
  • 1975-08-19 FR FR7525671A patent/FR2282489A1/fr active Granted
  • 1975-08-19 SE SE7509250A patent/SE410202B/xx unknown

Patent Citations (10)

Non-Patent Citations (2)

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